Method of manufacturing semiconductor device and semiconductor manufacturing apparatus

ABSTRACT

In one embodiment, a method of manufacturing a semiconductor device includes forming a first film on a substrate. The method further includes housing the substrate provided with the first film in a chamber, and introducing a first gas into the chamber. The method further includes generating plasma discharge of the first gas in the chamber or applying radiation to the first gas in the chamber. The method further includes introducing a second gas containing a metal component into the chamber to cause the metal component to infiltrate into the first film after the generation of the plasma discharge or the application of the radiation is started.

CROSS REFERENCE TO RELATED APPLICATION

This application is based upon and claims the benefit of priority fromthe prior Japanese Patent Application No. 2017-176082, filed on Sep. 13,2017, the entire contents of which are incorporated herein by reference.

FIELD

Embodiments described herein relate to a method of manufacturing asemiconductor device and a semiconductor manufacturing apparatus.

BACKGROUND

In a case of using an organic film as an etching mask, it is consideredto infiltrate a metal gas into the organic film to enhance etchingresistance of the organic film.

BRIEF DESCRIPTION OF THE DRAWINGS

FIGS. 1A to 2C are cross-sectional views illustrating a method ofmanufacturing a semiconductor device of a first embodiment;

FIGS. 3A to 3D are cross-sectional views illustrating a method ofmanufacturing a semiconductor device of a first comparative example ofthe first embodiment;

FIGS. 4A to 4D are cross-sectional views illustrating a method ofmanufacturing a semiconductor device of a second comparative example ofthe first embodiment;

FIGS. 5A to 7B are cross-sectional views illustrating operation of asemiconductor manufacturing apparatus of a second embodiment; and

FIGS. 8A to 10 are cross-sectional views illustrating operation of asemiconductor manufacturing apparatus of a third embodiment.

DETAILED DESCRIPTION

Embodiments will now be explained with reference to the accompanyingdrawings.

In one embodiment, a method of manufacturing a semiconductor deviceincludes forming a first film on a substrate. The method furtherincludes housing the substrate provided with the first film in achamber, and introducing a first gas into the chamber. The methodfurther includes generating plasma discharge of the first gas in thechamber or applying radiation to the first gas in the chamber. Themethod further includes introducing a second gas containing a metalcomponent into the chamber to cause the metal component to infiltrateinto the first film after the generation of the plasma discharge or theapplication of the radiation is started.

First Embodiment

FIGS. 1A to 2C are cross-sectional views illustrating a method ofmanufacturing a semiconductor device of a first embodiment.

First, an inter layer dielectric 2 is formed on a substrate 1 (FIG. 1A).Examples of the substrate 1 include semiconductor substrates such as asilicon (Si) substrate. Examples of the inter layer dielectric 2 includea silicon oxide film (SiO₂) and a silicon nitride film (SiN).

FIG. 1A illustrates an X direction and a Y direction that are parallelto a surface of the substrate 1 and are perpendicular to each other, anda Z direction that is perpendicular to the surface of the substrate 1.In the present specification, a +Z direction is handled as an upwarddirection, and a −Z direction is handled as a downward direction. The −Zdirection may be coincident with or not be coincident with a gravitydirection.

Next, a first base layer 3 is formed on the inter layer dielectric 2(FIG. 1A). The first base layer 3 is, for example, a spin on carbon(SOC) film having a thickness of 300 nm, and is formed by spin coating.The first base layer 3 may be directly formed on the substrate 1.

Next, a second base layer 4 is formed on the first base layer 3 (FIG.1A). The second base layer 4 is, for example, a spin on glass (SOG) filmhaving a thickness of 40 nm, and is formed by spin coating.

Next, an organic film 5 is formed on the second base layer 4 (FIG. 1A).The organic film 5 is a film containing carbon, and is, for example, apositive photoresist film. The organic film 5 of the present embodimenthas a thickness of 100 nm and is formed by spin coating. The organicfilm 5 is an example of a first film.

Next, the organic film 5 is processed to an organic film pattern 5 a(FIG. 1A). The organic film 5 is processed by, for example,photolithography using an ArF liquid immersion exposure apparatus. Theorganic film pattern 5 a is an example of a first pattern.

In a process of FIG. 1A, the organic film 5 may be processed to aplurality of the organic film patterns 5 a or to a single organic filmpattern 5 a. An example of the former includes that the organic patterns5 a become a plurality of line patterns, and openings in between theorganic film patterns 5 a become a plurality of space patterns. Anexample of the latter includes that openings in between the organic filmpattern 5 a become a plurality of hole patterns, and the organic filmpattern 5 a becomes a pattern surrounding the hole patterns. The organicfilm pattern 5 a of the present embodiment corresponds to the example ofthe latter, and a plurality of contact holes (C/Hs) are provided as thehole patterns.

Next, the substrate 1 is housed in a vacuum chamber (not illustrated),pressure inside the vacuum chamber is reduced to 10 Pa, and thesubstrate 1 is heated to 50° C. At this time, temperature of thesubstrate 1 is desirably varied within a range of 0° C. to 300° C.depending on a kind of a precursor described later, and dimensions anddensity of the openings in the organic film pattern 5 a.

Next, after the temperature of the substrate 1 is stabilized, an argon(Ar) gas is introduced into the vacuum chamber, and plasma discharge ofthe Ar gas is generated in the vacuum chamber. The Ar gas is an exampleof a first gas.

Next, after generation of the plasma discharge of the Ar gas is started,a metal gas is introduced into the vacuum chamber at pressure of 100 Pa,as illustrated by a reference sign “Km” (FIG. 1B). Examples of the metalgas include a trimethylaluminum (TMA) gas serving as an aluminumprecursor. The metal gas is an example of a second gas containing ametal component. The metal component in this case is a TMA molecule.

The metal gas of the present embodiment is introduced into the vacuumchamber while products (excited bodies) produced from the Ar gas existin the vacuum chamber. As a result, the metal gas is activated by theproducts produced from the Ar gas, and is made easy to infiltrate intothe organic film pattern 5 a. Examples of the products include Ar ionsand electrons.

As described above, in the present embodiment, the metal gas isindirectly activated through generation of the plasma discharge of theAr gas, instead of direct activation of the metal gas through generationof the plasma discharge of the metal gas. More specifically, the metalgas is mixed with the products produced from the Ar gas in the vacuumchamber, which causes energy of the products to move to the metal gas,thereby being activated.

According to the present embodiment, generation of the plasma dischargeof the Ar gas, not the metal gas, makes it possible to suppressdecomposition of the metal gas. Decomposition of the metal gas causes anissue that decomposed products from the metal gas contaminates thevacuum chamber to inhibit plasma enhanced chemical vapor deposition(PECVD) and plasma enhanced atomic layer deposition (PEALD). Accordingto the present embodiment, it is possible to suppress such the issue.

Next, to cause the metal gas to infiltrate into the entire organic film5, the substrate 1 is left to stand for five minutes after introductionof the metal gas is started (FIG. 1B). At this time, a standing time ofthe substrate 1 is desirably changed within a range of one minute to 120minutes depending on the kind of the precursor, and the dimensions andthe density of the openings in the organic film pattern 5 a.

Next, the pressure inside the vacuum chamber is reduced to 10 Pa, and asurplus TMA gas is discharged from the vacuum chamber (FIG. 1C).

Next, as illustrated by a reference sign “Ks”, steam is introduced intothe vacuum chamber at pressure of 250 Pa (FIG. 2A). The steam isintroduced in order to oxidize or reduce the metal components in theorganic film 5. In the present embodiment, the steam is introduced inorder to oxidize TMA. The steam is an example of a third gas.

Next, to sufficiently oxidize TMA in the organic film 5, the substrate 1is left to stand for three minutes after introduction of the steam isstarted (FIG. 2A).

Next, the pressure inside the vacuum chamber is reduced to 10 Pa,surplus steam is discharged from the vacuum chamber, and the substrate 1is cooled (FIG. 2B). As a result, the substrate 1 having the organicfilm pattern 5 a into which aluminum has been introduced is obtained. Inother words, the substrate 1 having the organic film pattern 5 ametalized by aluminum is obtained. The organic film pattern 5 a is usedas a mask for etching of the second base layer 4, etc.

In a case of FIG. 2B, aluminum is uniformly distributed into the organicfilm pattern 5 a. In contrast, in a case of FIG. 2C, aluminum isnon-uniformly distributed into the organic film pattern 5 a. FIG. 2Cillustrates a region R1 infiltrated with TMA and a region R2 notinfiltrated with TMA. Infiltration processing of the present embodimentmay be performed so as to obtain the organic film pattern 5 a of FIG.2B, or may be performed so as to obtain the organic film pattern 5 a ofFIG. 2C. In the case of FIG. 2C, it is sufficient for TMA to infiltrateto an extent allowing the organic film pattern 5 a to function as amask.

FIGS. 3A to 3D are cross-sectional views illustrating a method ofmanufacturing a semiconductor device of a first comparative example ofthe first embodiment.

First, as with FIG. 1A, the organic film 5 is formed on the second baselayer 4 (FIG. 3A). Next, the substrate 1 is housed in the vacuumchamber, and a metal gas is introduced into the vacuum chamber (FIG.3B). As a result, the metal gas infiltrates into the organic film 5.Examples of the metal gas include a TMA gas. Next, steam is introducedinto the vacuum chamber (FIG. 3C). As a result, TMA in the organic film5 is oxidized, and the substrate 1 having the organic film pattern 5 ametalized by aluminum is obtained.

The organic film pattern 5 a is used as a mask for etching of the secondbase layer 4, etc. In the present comparative example, however, theamount of TMA infiltrated into the organic film 5 is small, and etchingresistance of the organic film 5 is low. Therefore, the organic filmpattern 5 a is removed in etching (FIG. 3D).

In contrast, in the present embodiment, the large amount of TMAinfiltrates into the organic film 5 because the metal gas is indirectlyactivated, and the etching resistance of the organic film 5 isaccordingly enhanced. This makes it possible to prevent the organic filmpattern 5 a from being removed in etching.

FIGS. 4A to 4D are cross-sectional views illustrating a method ofmanufacturing a semiconductor device of a second comparative example ofthe first embodiment.

First, after the second base layer 4 is formed as with FIG. 1A, a resinfilm 6 is formed on the second base layer 4 (FIG. 4A). The resin film 6is, for example, a photocurable resin film having a thickness of 100 nm,and is formed by spin coating. Next, the resin film 6 is processed to aplurality of resin film patterns 6 a through imprinting using a quartzmold and ultraviolet irradiation of the resin film 6 (FIG. 4A). Examplesof the resin film patterns 6 a include a plurality of pillar patterns.The quartz mold is released from the resin film 6 after the resin film 6is cured through ultraviolet irradiation.

Next, a neutralized film (not illustrated) is formed on the second baselayer 4 by spin coating with use of the resin film 6 as a guide, and asurplus neutralized film is cleaned with cyclohexane. Next, an organicfilm 7 is formed on the second base layer 4 with the neutralized film inbetween with use of the resin film 6 as a guide (FIG. 4A). The organicfilm 7 is, for example, a polystyrene-polymethyl methacrylate copolymerfilm, and is formed by spin coating. Next, the organic film 7 is bakedat 230° C. to cause phase separation in the polystyrene-polymethylmethacrylate copolymer film to obtain a DSA (self-organized) film havinga thickness of 80 nm. As illustrated in FIG. 4A, an organic film pattern7 a composed of the organic film 7 is formed in between the resin filmpatterns 6 a. In FIG. 4A, one organic film pattern 7 a surrounds theplurality of resin film patterns 6 a.

Next, the substrate 1 is housed in the vacuum chamber, and a metal gasis introduced into the vacuum chamber (FIG. 4B). As a result, the metalgas infiltrates into the organic film 7. Examples of the metal gasinclude a TMA gas. Next, steam is introduced into the vacuum chamber(FIG. 4C). As a result, TMA in the organic film 7 is oxidized, and thesubstrate 1 having the organic film pattern 7 a metalized by aluminum isobtained.

The organic film pattern 7 a is used as a mask for etching of the secondbase layer 4, etc. In the present comparative example, however, theamount of TMA infiltrated into the organic film 7 is small, and etchingresistance of the organic film 7 is low. Therefore, the organic filmpattern 7 a is removed in etching (FIG. 4D).

In contrast, in the present embodiment, the large amount of TMAinfiltrates into the organic film 5 because the metal gas is indirectlyactivated, and the etching resistance of the organic film 5 isaccordingly enhanced. This makes it possible to prevent the organic filmpattern 5 a from being removed in etching. The method of the presentembodiment is applicable to the organic film 7 of the second comparativeexample as described later.

(Modifications of First Embodiment)

In the above description, the example of the organic film 5 is aphotoresist film, the example of the metal gas is a TMA gas, and theexample of the plasma discharge condition is 50° C. for five minutes. Inthis case, according to an experiment, a metal content of the organicfilm 5 was 32%. When the plasma discharge condition was changed to 100°C. for five minutes, the metal content of the organic film 5 was 36%.Further, when the plasma discharge condition was changed to 50° C. fortwo minutes, the metal content of the organic film 5 was 30%. Asdescribed above, it was made clear that the present embodiment providesthe organic film 5 having a preferred metal content.

The organic film 5, the metal gas, and the plasma discharge condition ofthe present embodiment, however, are not limited to these examples. Inthe following, various modifications of the present embodiment aredescribed.

In a first modification, the organic film 5 was replaced with theorganic film 7, a TMA gas was used as the metal gas, and the plasmadischarge condition was set to 50° C. for five minutes. In this case,according to the experiment, a metal content of the organic film 7 was34%. When the plasma discharge condition was changed to 120° C. for fiveminutes, the metal content of the organic film 7 was 38%. Further, whenthe plasma discharge condition was changed to 50° C. for two minutes,the metal content of the organic film 7 was 29%.

In a second modification, an SOC film was used as the organic film 5, aTMA gas was used as the metal gas, and the plasma discharge conditionwas set to 200° C. for ten minutes. In this case, according to theexperiment, the metal content of the organic film 5 was 22%. When theplasma discharge condition was changed to 150° C. for ten minutes, themetal content of the organic film 5 was 17%. Further, when the plasmadischarge condition was changed to 100° C. for 30 minutes, the metalcontent of the organic film 5 was 18%.

In a third modification, an amorphous carbon film (APF) was used as theorganic film 5, a TMA gas was used as the metal gas, and the plasmadischarge condition was set to 200° C. for 30 minutes. In this case,according to the experiment, the metal content of the organic film 5 was24%. When the plasma discharge condition was changed to 200° C. for tenminutes, the metal content of the organic film 5 was 20%. Further, whenthe plasma discharge condition was changed to 150° C. for 30 minutes,the metal content of the organic film 5 was 21%.

In a fourth modification, a photoresist film was used as the organicfilm 5, a WF₆ (tungsten hexafluoride) gas was used as the metal gas, andthe plasma discharge condition was set to 250° C. for five minutes. Inthis case, according to the experiment, the metal content of the organicfilm 5 was 18%.

In a fifth modification, a photoresist film was used as the organic film5, a TDMAT (tetrakis dimethylamino titanium) gas was used as the metalgas, and the plasma discharge condition was set to 250° C. for fiveminutes. In this case, according to the experiment, the metal content ofthe organic film 5 was 23%.

In a sixth modification, a photoresist film was used as the organic film5, a PDMAT (pentakis(dimethylamino)tantalum) gas was used as the metalgas, and the plasma discharge condition was set to 200° C. for fiveminutes. In this case, according to the experiment, the metal content ofthe organic film 5 was 26%.

In a seventh modification, a photoresist film was used as the organicfilm 5, a RDE ((2,4-dimethylpentadienyl)(ethylpentadienyl)ruthenium) gaswas used as the metal gas, and the plasma discharge condition was set to150° C. for ten minutes. In this case, according to the experiment, themetal content of the organic film 5 was 21%.

In these modifications, plasma discharge of the Ar gas is generated inthe vacuum chamber to indirectly activate the metal gas. In contrast, ineighth and ninth modifications described later, radiation is applied tothe Ar gas in the vacuum chamber to indirectly activate the metal gas.Examples of such radiations include particle beams such as electronbeams, and electromagnetic waves such as light rays and ultravioletrays. A method of setting temperature in radiation application and amethod of setting start timing and end timing of the radiationapplication are similar to those in the plasma discharge.

In the eighth modification, a photoresist film was used as the organicfilm 5, a TMA gas was used as the metal gas, and an electron beamirradiation condition was set to 50° C. for five minutes. In this case,according to the experiment, the metal content of the organic film 5 was31%. When the electron beam irradiation condition was changed to 100° C.for ten minutes, the metal content of the organic film 5 was 32%.Further, when the electron beam irradiation condition was changed to 50°C. for two minutes, the metal content of the organic film 5 was 27%.

In the ninth modification, the organic film 5 was replaced with theorganic film 7, a TMA gas was used as the metal gas, and the electronbeam irradiation condition was set to 50° C. for five minutes. In thiscase, according to the experiment, the metal content of the organic film7 was 31%. When the electron beam irradiation condition was changed to120° C. for five minutes, the metal content of the organic film 7 was31%. Further, when the electron beam irradiation condition was changedto 50° C. for two minutes, the metal content of the organic film 7 was27%.

According to the experiments, in a case of adopting the method of thepresent embodiment and the modifications thereof, it was made clear thatthe organic film 5 (or organic film 7) having a preferred metal contentis obtainable under the plasma discharge condition or the radiationirradiation condition at low temperature for a short time.

As described above, in the present embodiment, the Ar gas is activatedthrough the plasma discharge or the radiation application, and the metalgas is activated with use of the Ar gas. Therefore, according to thepresent embodiment, it is possible to appropriately promote infiltrationof the metal gas into the organic film 5. For example, it is possible topromote infiltration of the metal gas into the organic film 5 whilesuppressing decomposition of the metal gas. As a result, it is possibleto form the organic film 5 having high etching resistance by theprocessing at low temperature for a short time, which allows forreduction of the manufacturing cost of the semiconductor device.

The gas as a target of the plasma discharge and the radiationapplication may be a gas other than the Ar gas. Examples of such a gasinclude noble gases other than the Ar gas.

Second Embodiment

FIGS. 5A to 7B are cross-sectional views illustrating operation of asemiconductor manufacturing apparatus of a second embodiment.

The semiconductor manufacturing apparatus of the present embodiment isused to perform the plasma discharge and the metallization in the firstembodiment. As illustrated in FIG. 5A, the semiconductor manufacturingapparatus includes a chamber 11, a stage 12, a heater 13, a plasmasource 14, a first gas introduction module 15, a second gas introductionmodule 16, a steam introduction module 17, a discharge module 18, and acontroller 19.

The chamber 11 includes a first portion 11 a housing the substrate 1including the organic film pattern 5 a and a second portion 11 bprotruding from the first portion 11 a. FIG. 5A illustrates a statewhere a wafer “W” composed of the substrate 1, the inter layerdielectric 2, the organic film pattern 5 a, and the like is housed inthe first portion 11 a. The chamber 11 is used as the vacuum chamberdescribed in the first embodiment. The Ar gas, the metal gas, and thesteam are introduced into the second portion 11 b, and flow from thesecond portion 11 b into the first portion 11 a.

The stage 12 supports the substrate 1 in the chamber 11. The stage 12can vertically move the substrate 1. This facilitates carrying thesubstrate 1 into and out of the semiconductor manufacturing apparatus.

The heater 13 configures a part of the stage 12, and can heat thesubstrate 1 on the stage 12.

The plasma source 14 is a mechanism generating the plasma discharge ofthe Ar gas in the second portion 11 b. The products (excited bodies)produced from the Ar gas in the second portion 11 b enter the firstportion 11 a from the second portion 11 b. The excited bodies, however,are deactivated before reaching the substrate 1 because the secondportion 11 b of the present embodiment is sufficiently separated fromthe stage 12. The plasma source 14 is an example of a gas processingmodule.

The first gas introduction module 15 is located in the second portion 11b, and introduces the Ar gas into the second portion 11 b. The secondgas introduction module 16 is located in the second portion 11 b, andintroduces the metal gas into the second portion 11 b. The steamintroduction module 17 is located in the second portion 11 b, andintroduces the steam into the second portion 11 b. The discharge module18 is located in the first portion 11 a, and discharges the gas from thechamber 11 to outside. An intake mechanism (not illustrated) to take inthe gas from the chamber 11 is connected to the discharge module 18.

The first gas introduction module 15 is located at a first distance fromthe stage 12, and the second gas introduction module 16 is located at asecond distance from the stage 12 which is smaller than the firstdistance. In other words, the second distance between the second gasintroduction module 16 and the stage 12 is smaller than the firstdistance between the first gas introduction module 15 and the stage 12.

Accordingly, the Ar gas that has been introduced from the first gasintroduction module 15 into the second portion 11 b is changed toexcited bodies. The excited bodies subsequently pass through a regionwhere the metal gas exists in high concentration, and then enter thefirst portion 11 a. This makes it possible to efficiently move theenergy of the excited bodies to the metal gas.

The first distance between the first gas introduction module 15 and thestage 12 is set to a distance that deactivates the excited bodies beforethe excited bodies reach the organic film pattern 5 a. This makes itpossible to suppress the excited bodies from adversely affecting theorganic film pattern 5 a.

The controller 19 controls various operation of the semiconductormanufacturing apparatus. The controller 19 controls, for example,vertical movement of the stage 12, temperature of the heater 13,operation of the plasma source 14, gas introduction from the first gasintroduction module 15, the second gas introduction module 16, and thesteam introduction module 17, and a gas discharge from the dischargemodule 18. The controller 19 of the present embodiment controlsoperation of the heater 13 so as to vary the temperature of thesubstrate 1 within a range of 0° C. to 300° C. Examples of thecontroller 19 include a processor, an electric circuit, and a computer.

The operation of the semiconductor manufacturing apparatus of thepresent embodiment is described below.

First, after the substrate 1 (wafer “W”) is housed in the first portion11 a, the Ar gas is introduced from the first gas introduction module 15into the second portion 11 b, and the plasma source 14 generates theplasma discharge of the Ar gas (FIG. 5A). White triangles illustrated inFIG. 5A indicate Ar atoms and Ar plasma produced from the Ar atoms.Further, a reference sign “P” schematically illustrates a region wherethe plasma discharge is generated.

Next, after generation of the plasma discharge is confirmed, the metalgas is introduced from the second gas introduction module 16 into thesecond portion 11 b (FIG. 5B). Black triangles illustrated in FIG. 5Bindicate TMA molecules in the metal gas. The TMA molecules collide withion species of the Ar plasma flowing from upstream side, thereby beingenergetically activated (FIG. 5C).

The activated TMA molecules arrive at the vicinity of the substrate 1(FIGS. 6A and 6B). In contrast, the Ar plasma is deactivated beforearriving at the vicinity of the substrate 1 due to collision with theTMA molecules and the distance between the first gas introduction module15 and the stage 12, and returns to normal Ar atoms. This makes itpossible to suppress collision of the Ar plasma with the organic filmpattern 5 a. Dotted triangles illustrated in FIGS. 6A and 6B indicatethe Ar atoms deactivated from the Ar plasma. In the present embodiment,the distance between the plasma source 14 and the substrate 1 is largein order to promote deactivation of the Ar plasma, and is specificallyset to 30 cm.

Next, to cause the metal gas arriving at the organic film pattern 5 a toinfiltrate into the organic film pattern 5 a, the state is maintainedfor five minutes (FIG. 6C). Next, to oxidize TMA in the organic filmpattern 5 a, steam is introduced from the steam introduction module 17into the second portion 11 b, and the state is maintained for threeminutes (FIG. 7A).

Next, the pressure inside the chamber 11 is reduced to 10 Pa, surplussteam is discharged through the discharge module 18, and further thesubstrate 1 is cooled (FIG. 7B). In the present embodiment, thesubstrate 1 is cooled by stopping the heater 13 or reducing thetemperature of the heater 13. As a result, the substrate 1 having theorganic film pattern 5 a into which aluminum has been introduced isobtained.

The semiconductor manufacturing apparatus of the present embodimentmakes it possible to appropriately promote infiltration of the metal gasinto the organic film 5 when the method of the first embodiment isperformed.

Third Embodiment

FIGS. 8A to 10 are cross-sectional views illustrating operation of asemiconductor manufacturing apparatus of a third embodiment.

The semiconductor manufacturing apparatus of the present embodiment isused to perform the radiation application and the metallization in themodifications of the first embodiment. As illustrated in FIG. 8A, thesemiconductor manufacturing apparatus includes a chamber 21, a stage 22,a heater 23, a radiation source 24, a first gas introduction module 25,a second gas introduction module 26, a steam introduction module 27, adischarge module 28, and a controller 29. The chamber 21 includes afirst portion 21 a and a second portion 21 b. Functions of therespective modules are similar to the corresponding modules of thesemiconductor manufacturing apparatus of the second embodiment exceptfor the radiation source 24.

The radiation source 24 is a mechanism to apply radiation (electronbeams in this case) to the Ar gas in the second portion 21 b. Theproducts (excited bodies) produced from the Ar gas in the second portion21 b enter the first portion 21 a from the second portion 21 b. As withthe second embodiment, the excited bodies are deactivated beforearriving at the substrate 1 because the second portion 21 b of thepresent embodiment is sufficiently separated from the stage 22. Theradiation source 24 is an example of the gas processing module.

Operation of the semiconductor manufacturing apparatus of the presentembodiment is described below.

First, after the substrate 1 (wafer “W”) is housed in the first portion21 a, the Ar gas is introduced from the first gas introduction module 25into the second portion 21 b (FIG. 8A), and the radiation source 24applies electron beams to the Ar gas (FIG. 8B). White trianglesillustrated in FIGS. 8A and 8B indicate Ar atoms and Ar ion speciesproduced from the Ar atoms. The Ar atoms are ionized by electron beamapplication and are highly activated.

Next, the metal gas is introduced from the second gas introductionmodule 26 into the second portion 21 b (FIG. 8C). Black trianglesillustrated in FIG. 8C indicate TMA molecules in the metal gas. The TMAmolecules collide with Ar ions flowing from upstream side, thereby beingenergetically activated (FIG. 8C).

The activated TMA molecules arrive at the vicinity of the substrate 1(FIG. 9A). In contrast, the Ar ions are deactivated before arriving atthe vicinity of the substrate 1 due to collision with the TMA moleculesand the distance between the first gas introduction module 25 and thestage 22, and return to normal Ar atoms. This makes it possible tosuppress collision of the Ar ions with the organic film pattern 5 a.Dotted triangles illustrated in FIG. 9A indicate the Ar atomsdeactivated from the Ar ions. In the present embodiment, the distancebetween the radiation source 24 and the substrate 1 is large in order topromote deactivation of the Ar ions, and is specifically set to 30 cm.

Next, to cause the metal gas arriving at the organic film pattern 5 a tofiltrate into the organic film pattern 5 a, the state is maintained forfive minutes (FIG. 9B). Next, to oxidize TMA in the organic film pattern5 a, steam is introduced from the steam introduction module 27 into thesecond portion 21 b, and the state is maintained for three minutes (FIG.9C).

Next, the pressure inside the chamber 21 is reduced to Pa, surplus steamis discharged through the discharge module 28, and further the substrate1 is cooled (FIG. 10). In the present embodiment, the substrate 1 iscooled by stopping the heater 23 or reducing the temperature of theheater 23. As a result, the substrate 1 having the organic film pattern5 a into which aluminum has been introduced is obtained.

The semiconductor manufacturing apparatus of the present embodimentmakes it possible to appropriately promote infiltration of the metal gasinto the organic film 5 when the method in the modifications of thefirst embodiment is performed.

While certain embodiments have been described, these embodiments havebeen presented by way of example only, and are not intended to limit thescope of the inventions. Indeed, the novel methods and apparatusesdescribed herein may be embodied in a variety of other forms;furthermore, various omissions, substitutions and changes in the form ofthe methods and apparatuses described herein may be made withoutdeparting from the spirit of the inventions. The accompanying claims andtheir equivalents are intended to cover such forms or modifications aswould fall within the scope and spirit of the inventions.

1. A method of manufacturing a semiconductor device, comprising: forminga first film on a substrate; housing the substrate provided with thefirst film in a chamber; introducing a first gas into the chamber;generating plasma discharge of the first gas in the chamber or applyingradiation to the first gas in the chamber; and introducing a second gascontaining a metal component into the chamber to cause the metalcomponent to infiltrate into the first film after the generation of theplasma discharge or the application of the radiation is started.
 2. Themethod of claim 1, wherein the substrate is housed in the chamber aftera first pattern is formed on the first film, and the metal componentinfiltrates into the first pattern.
 3. The method of claim 1, whereinthe first gas is a noble gas.
 4. The method of claim 1, wherein thesecond gas is introduced into the chamber that contains a productproduced from the first gas.
 5. The method of claim 1, furthercomprising introducing, into the chamber, a third gas that oxidizes orreduces the metal component infiltrated into the first film.
 6. Themethod of claim 1, wherein the first film is a film containing carbon.7. The method of claim 1, wherein the first film includes at least oneof a photoresist film, a self-organized film, a spin on carbon film andan amorphous carbon film.
 8. The method of claim 1, wherein the firstgas is introduced into the chamber from a first gas introduction modulelocated at a first distance from a stage that supports the substrate,and the second gas is introduced into the chamber from a second gasintroduction module located at a second distance from the stage, thesecond distance being smaller than the first distance.
 9. The method ofclaim 8, wherein the first distance is a distance deactivating a productproduced from the first gas before the product arrives at the firstfilm.
 10. The method of claim 1, wherein the chamber includes a firstportion housing the substrate, and a second portion into which the firstand second gases are introduced, the second portion protruding from thefirst portion.
 11. A semiconductor manufacturing apparatus comprising: achamber that houses a substrate provided with a first film; a first gasintroduction module that introduces a first gas into the chamber; a gasprocessing module that generates plasma discharge of the first gas inthe chamber or applies radiation to the first gas in the chamber; and asecond gas introduction module introduces a second gas containing ametal component into the chamber to cause the metal component toinfiltrate into the first film.
 12. The apparatus of claim 11, whereinthe substrate is housed in the chamber after a first pattern is formedon the first film, and the metal component infiltrates into the firstpattern.
 13. The apparatus of claim 11, wherein the first gas is a noblegas.
 14. The apparatus of claim 11, wherein the second gas is introducedinto the chamber that contains a product produced from the first gas.15. The apparatus of claim 11, further comprising a third gasintroduction module that introduces, into the chamber, a third gas thatoxidizes or reduces the metal component infiltrated into the first film.16. The apparatus of claim 11, wherein the first film is a filmcontaining carbon.
 17. The apparatus of claim 11, wherein the first filmincludes at least one of a photoresist film, a self-organized film, aspin on carbon film and an amorphous carbon film.
 18. The apparatus ofclaim 11, wherein the first gas introduction module is located at afirst distance from a stage that supports the substrate, and the secondgas introduction module is located at a second distance from the stage,the second distance being smaller than the first distance.
 19. Theapparatus of claim 18, wherein the first distance is a distancedeactivating a product produced from the first gas before the productarrives at the first film.
 20. The apparatus of claim 11, wherein thechamber includes a first portion housing the substrate, and a secondportion into which the first and second gases are introduced, the secondportion protruding from the first portion.